An inter-calibration campaign using various selected Pu spike isotopic reference materials

In nuclear safeguards, precise and accurate isotopic analyses are needed for two major elements from the nuclear fuel cycle: uranium and plutonium. This can be achieved by Isotope Dilution Mass Spectrometry (IDMS), which is one of the most reliable analytical techniques for the determination of plutonium amount content to a high level of accuracy. In order to achieve reliable isotope measurements isotopic reference materials with certified amount of plutonium and isotopic composition are required. At the Institute for Reference Materials and Measurements (IRMM) various plutonium spike reference materials for isotopes ²³⁹Pu, ²⁴⁰Pu, ²⁴²Pu and ²⁴⁴Pu are available. This enabled the setup of an inter-calibration campaign inter-linking selected plutonium spikes on a metrological basis applying state-of-the-art measurement procedures. The aim of this campaign is threefold: firstly to perform measurements on selected plutonium spike isotopic reference materials for quality control purposes, secondly to verify the amount content and the isotopic composition of the recently produced IRMM-1027m large sized dried (LSD) spikes and thirdly to demonstrate IRMM’s measurement capabilities for plutonium analysis via external quality tools. The obtained results using various spike isotopic reference materials will be presented and discussed in this paper. The measurement uncertainties of the IDMS results were calculated according to the guide to the expression of uncertainty in measurement (GUM).     

Reverse isotope dilution alpha spectrometry using plutionium-239 spike for determining plutonium concentration in high burn-up fuel samples without purification from americium-241 and a bulk of other impurities

A reverse isotope dilution alpha spectrometric /R-IDAS/ method using²³⁹Pu as a spike is described for the determination of plutonium concentration in high burn-up fuel samples wth²³⁸Pu/(²³⁹Pu+²⁴⁰Pu) alpha activity ratio >0.5, without resorting to any purification from²⁴¹Am and a bulk of other impurities. It involves the addition of a pre-clibrated spike solution to a known aliquot of the plutonium sample solution followed by source preparation using TEG as a spreading agent. The results obtained on a number of plutonium samples containing 20–80% of²⁴¹Am /alpha activity wise/ using this method are compared with those achieved by R-IDAS using purification with TTA, with respect to precision and accuracy. Precision and accuracy of 0.5% are demonstrated. This method eliminates the need of any separation and purification of plutonium from²⁴¹Am and a bulk of other impurities like uranium.     

Determination of femtogram quantities of 239Pu and 240Pu in bioassay samples by thermal ionization mass spectrometry

Summary A thermal ionization mass spectrometry (TIMS) method is described for the determination of ultra-trace levels of plutonium isotopes in human urine samples. The method has been validated through the analysis of artificial urine samples spiked with known amounts of ²³⁹Pu ranging from 2.5 fg to 50 fg (6-115mBq). A slight positive bias of 1.7%-2.7% was determined, with a relative precision of 2.2% at 50 fg, increasing to 2.7% for 5-25 fg ²³⁹Pu. The detection limit of the method was 0.53 fg (1.2mBq) ²³⁹Pu, and the instrumental detection limit was at least 0.1 fg. The determination of the isotopic signature of the sample with ²³⁹Pu, ²⁴⁰Pu, and ²⁴¹Pu amounts of several femtograms is possible, and was demonstrated with the determination of the 240 to 239 ratio in an inter-laboratory sample comparison. The method is relatively free from interferences, 95% of sample preparations were acceptable both in terms of chemical recovery and lack of isobaric interference. The isotopic abundance of the ²⁴²Pu SRM 4334E of the National Institute of Standards and Technology (NIST) was also determined by TIMS and was found to be 99.99967 atom% ²⁴²Pu.     

Plutonium concentration distribution in bed load sediment samples along the Romanian sector of the Danube river and the Black Sea coast

The concentrations of²³⁸Pu and^{239, 240}Pu were determined in 12 sediment samples collected from the bed of the Romanian Danube river and Black Sea coast during June–September 1994. After the sample material has been properly prepared and²⁴²Pu tracer added, plutonium was separated from americium and curium by anion exchange. After electrodeposition on stainless steel discs the elements were counted with an -spectrometry system with silicon surface-barrier detectors. The^{239, 240}Pu concentrations range between 150 and 800 mBq kg^–1 dry, while the²³⁸Pu concentrations rise up to max 150 mBq kg^–1 dry. Although the chemical yields are rather low (51%) we appreciate the results as valuable since they report for the first time the distribution of the plutonium contamination along the Danube river and the Black Sea coast-Romanian sector.     

Half-life of plutonium-241: Past and present

Half-life of²⁴¹Pu is of great importance in nuclear technology. In view of large variation in the values (13–15 y) reported till 1974 in literature, efforts have been made in different laboratories to determine this half-life with high precision and accuracy. In our laboratory, it has been determined by different methods which may be classified in two categories, viz. (1) parent decay method, and (2) daughter growth method. In the parent decay method, change in isotope ratios²⁴¹Pu/²³⁹Pu,²⁴¹Pu/²⁴⁰Pu and²⁴¹Pu/²⁴²Pu was studied periodically by a thermal ionization mass spectrometer. Single as well as double ratio method was used to calculate the half-life. In the daughter growth method, the half-life was obtained in four independent ways. These were (1) alpha spectrometry taking²³⁹Pu and²⁴²Pu separately as reference isotopes and studying periodically the increase in alpha activity ratio, (2) alpha proportional counting for observing periodically the change in total alpha activity, (3) isotope dilution alpha spectrometry using²⁴³Am as a spike, (4) isotope dilution mass spectrometry using²⁴³Am as a spike. In all these methods, synthetic mixtures were prepared for achieving high precision and accuracy in different measurements. Based on the results obtained in this laboratory and the values reported by other laboratories, a half-life value of 14.4±0.1 y is recommended. The paper reviews the past history, puts forth the present status, highlights the current trends for studying the effect of chemical composition of plutonium on the half-life of²⁴¹Pu and presents the future requirements for achieving higher accuracy in the half-life of²⁴¹Pu.     

Experimental evaluation of239Pu,238Pu and233U spikes for determining plutonium concentration by thermal ionization mass spectrometry and alpha-spectrometry

Experimental evaluation on the use of²³⁹Pu spike in Isotope Dilution-Thermal Ionization Mass Spectrometry (ID-TIMS),²³⁸Pu spike in Isotope Dilution Alpha Spectrometry (IDAS) and²³³U as a Non-Isotopic Diluent in Alpha Spectrometry (N-IDAS), for determing plutonium concentration in samples with burn-up values in the range of 1,000–10,000 MWD/TU is done. Precision is determined by analyzing replicate aliquots from different samples using each of the three spikes. Accuracy is established by comparing the results with those obtained by using well recognized spike²⁴²Pu in ID-TIMS. It is shown that the use of²³⁹Pu spike with the latest generation thermal ionization mass spectrometers gives the best precision (0.2%), whereas the precision values of 0.5 and 1% can be obtained by using²³⁸Pu and²³³U spikes, respectively, on a routine basis. Reasons for the difference in the precision values are discussed, along with the merits and drawbacks on the use of different spike isotopes.     

A gamma-spectrometric method for the determination of plutonium isotope ratios

A gamma-spectrometric method using an intrinsic high resolution germanium detector has been developed for the determination of isotope ratios of plutonium from samples in solution form. The method is based on the assay of low energy gamma-rays of²³⁸Pu,²³⁹Pu,²⁴⁰Pu and²⁴¹Pu and does not require the use of branching intensities or the knowledge of detection efficiencies for different gamma rays. Since low energy gamma-rays are used, the effect of²⁴¹Am has also been studied. It is found that results are not affected up to 0.5 wt% of²⁴¹Am in plutonium samples. An accuracy of 3% is achievable in the determination of²⁴⁰Pu/²³⁹Pu and²⁴¹Pu/²³⁹Pu atom ratios as demonstrated by carrying out measurements on isotopic standards of plutonium.     

Determination of the plutonium concentration by Isotope Dilution Alpha-Spectrometry without purification from americium-241 and a bulk of other impurities

Summary A method is described for determining the plutonium concentration by Isotope Dilution Alpha Spectrometry (IDAS) using²³⁸Pu as a spike. It involves the addition of a pre-calibrated spike solution to a known aliquot of the plutonium sample solution followed by source preparation using TEG as a spreading agent. The results obtained on a number of samples using this method are compared with those of IDMS using²⁴²Pu as a spike as well as with those obtained by IDAS using TTA for purification, with respect to precision and accuracy. Precision of 0.3–0.5% and an accuracy of 0.5% is demonstrated. This method eliminates the need of any separation and purification of plutonium from²⁴¹ Am and a bulk of other impurities.

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Plutoniumbestimmung durch Isotopenverdünnungs-Alpha-Spektrometrie ohne Abtrennung von Americium-241 und anderen Verunreinigungen

Zusammenfassung Bei dem beschriebenen Verfahren der Isotopenverdünnungs-Alpha-Spektrometrie (IDAS) wird²³⁸Pu als Spike benutzt. Eine vorgeeichte Spike-Lösung wird zu einem bekannten Aliquot der Probe gegeben und anschließend die Strahlungsquelle unter Verwendung von Tetraethylenglykol als Spreading-Reagens vorbereitet. Die nach diesem Verfahren erhaltenen Ergebnisse werden in bezug auf Präzision und Genauigkeit mit solchen verglichen, die mit Isotopenverdünnungs-Massenspektrometrie unter Verwendung von²⁴²Pu als Spike oder mit IDAS unter Verwendung von Thenoyltrifluoraceton zur Reinigung erhalten wurden. Eine Präzision von 0,3–0,5% und eine Genauigkeit von 0,5% wurden erzielt. Durch das beschriebene Verfahren erübrigt sich eine Reinigung des Pu von²⁴¹Am und anderen Verunreinigungen.

     

Simultaneous determination of238Pu,239+240Pu,241Pu,241Am,242Cm,244Cm,89Sr,and90Sr in vegetation samples,and application to Chernobyl-fallout contaminated grass

A radiochemical procedure is described for the simultaneous determination of²³⁸Pu,^239+240Pu,²⁴¹Pu,²⁴¹Am,²⁴²Cm,²⁴⁴Cm,⁸⁹Sr, and⁹⁰Sr in vegetation samples. The method was applied for the determination of these, radionuclides in grass, collected near Munich after the fallout from the reactor accident at Chernobyl, USSR. The specific activities observed were (in Bq kg^–1 dry weight):²³⁸Pu, 0.077;^239+240Pu, 0.15;²⁴¹Pu, 3.9;²⁴¹Am, 0.031;²⁴²Cm, 3.0;²⁴⁴Cm, 0.008;⁸⁹Sr, 2000;⁹⁰Sr, 99.     

Determination of plutonium,americium and curium in airborne effluents of nuclear power plants

A radiochemical method has been developed for the determination of²³⁸Pu,^{239, 240}Pu,²⁴¹Am,²⁴²Cm and²⁴⁴Cm in airborne effluents of nuclear power plants. The method involves conversion of transuranium elements to acid-soluble forms, dissolution, purification, electrodeposition and alpha spectrometric determination. Final recovery ranged from 69.0 to 75.4% for plutonium and from 26.8 to 68.3% for americium and curium.     

Radiochemical determination of the yields of transuranium nuclides produced from natural uranium irradiated in a reactor

Transuranium nuclides were produced by irradiating a pellet of natural uranium sulfide in the Japan Material Testing Reactor (JMTR). After irradiation, a successive separation of uranium, plutonium, americium and curium was carried out. The fractional concentrations of the nuclides²³⁸Pu,²³⁹Pu,²⁴⁰Pu,²⁴¹Am,²⁴³Am,²⁴²Cm and²⁴⁴Cm were determined by α-ray spectrometry, and those of²⁴¹Pu and^242mAm were estimated from the build-up of α-emitting daughters,²⁴¹Am and²⁴²Cm, respectively. As the yield of²⁴²Pu was too slight to be detected by α-counting, the neutron activation analysis of the plutonium fraction based on the²⁴²Pu(n, γ)²⁴³Pu reaction was carried out by γ-ray spectrometry, and it was shown that a few pg of²⁴²Pu could be determined. A burn-up of²³⁵U was also estimated by neutron activation analysis. The experimental results are compared with the calculated ones.     

The isotopic composition of plutonium in the National Institute of Standards and Technology Standard Reference Material 4351, human lung

The Standard Reference Material 4351 from the National Institute of Standards and Technology is acknowledged to be inhomogeneous. The value of a single analysis for²³⁹Pu+²⁴⁰Pu could lie within a wide range, but the accuracy of the analysis can be corroborated by comparing the corresponding²³⁸Pu/²³⁹Pu+²⁴⁰Pu or²⁴⁰Pu/239Pu values with the relationships between these ratios and the total plutonium concentration.     

Separation of plutonium from uranium using reactive chemistry in a bandpass reaction cell of an inductively coupled plasma mass spectrometer

Oxygen and ammonia were evaluated as reaction gases for the chemical separation between uranium and plutonium in the bandpass reaction cell or dynamic reaction cell (DRC) of the ELAN DRC II mass spectrometer. Both uranium and plutonium demonstrated similar reactivity with oxygen giving rise to corresponding oxides. At the same time, remarkable selectivity in the reaction with ammonia was observed. While uranium was rapidly converted into UNH ₂⁺ and UN₂H ₄⁺ , plutonium remained unreactive in the DRC pressurized with ammonia. This difference in the reactivity allowed the determination of plutonium isotopes in urine and water samples containing excess uranium without preceding separation procedure. Detection limits of 0.245, 0.092, 0.270 and 0.237 ng L^–1 were obtained for ²³⁸Pu, ²³⁹Pu, ²⁴⁰Pu and ²⁴²Pu, respectively, in urine spiked with 10 g L^–1 of U.     

Determination of plutonium activity concentrations and <Superscript>240</Superscript>Pu/<Superscript>239</Superscript>Pu atom ratios in Brown Algae (<Emphasis Type="Italic">Fucus distichus</Emphasis>) collected from Amchitka Island,Alaska

Plutonium-239 (²³⁹Pu) and plutonium-240 (²⁴⁰Pu) activity concentrations and ²⁴⁰Pu/²³⁹Pu atom ratios are reported for Brown Algae (Fucus distichus) collected from the littoral zone of Amchitka Island (Alaska), and at a control site at Unalaska, Alaska. The average ²⁴⁰Pu/²³⁹Pu atom ratio observed in dried F. distichus collected from Amchitka Island was 0.227 ± 0.007 (N = 5) and compares with the expected ²⁴⁰Pu/²³⁹Pu atom ratio in integrated worldwide fallout deposition in the Northern Hemisphere of 0.1805 ± 0.0057. In the absence of any evidence of a local source of plutonium containing an elevated ²⁴⁰Pu/²³⁹Pu isotopic signature, the characteristically high ²⁴⁰Pu/²³⁹Pu content of F. distichus supports the view of the existence of a discernible, basin-wide non-fallout source of plutonium entering the subarctic Pacific.     

Identification of the contamination source of plutonium in environmental samples with isotopic ratios determined by inductively coupled plasma mass spectrometry and alpha-spectrometry

Concentrations of^239+249Pu in environmental samples were detemined by ICP-MS and spectrometry, showing consistent results, which suggests an applicability of ICP-MS to²³⁹Pu and²⁴⁰Pu measurement. The activity ratios of²³⁸Pu/^239+240Pu and²⁴⁰Pu/²³⁹Pu were significantly different in samples from the general environment and near Sellafield reprocessing plants, indicating the usefulness of these ratios for identification of the Pu contamination source.     

Procedures to define Pu isotopic ratios characterizing a contaminated area in Palomares (Spain)

Plutonium isotopic ratios have been calculated in soils contaminated by the Palomares accident which occurred in 1966 (Almería, Southeastem Spain). Contrasted techniques have been used to determine the radionuclide activities:²³⁸Pu and^238+240Pu were analysed by -spectrometry prior purification on anion-exchange resins, the ratio²³⁹Pu/²⁴⁰Pu was estimated by -spectra deconvolution and²⁴¹Pu was directly measured by liquid scintillation counting and indirectly through quantification of in-grown²⁴¹Am from aged plutonium discs. The mean activity ratios²³⁸Pu/²³⁹Pu,²³⁹Pu/²⁴⁰Pu,²⁴¹Pu/²³⁹Pu, backdated to 1966, were 0.027±0.002 (1), 4.5±0.2 (1) and 8.2±0.8 (1), respectively, characterizing the accident of Palomares as the source term of the measured plutonium.     

Plutonium in lungs and livers of persons from Chernobyl fallout affected areas in Byelorussia

^239+240Pu and-when possible-also the ratio²³⁸Pu/^239+240Pu was determined in the lungs and livers of 15 residents from Chernobyl-fallout contaminated areas in Byelorussia. In several cases various sections of the lungs were analyzed separately. With the exception of one person the activity concentrations of^239+240Pu, were always within the range expected from the global fallout of weapon tests in the sixties and did not indicate any contribution of Chernobyl-derived plutonium.     

Low-level determination of plutonium by gamma and L X-ray spectroscopy

We have developed an analytical method for detection of²³⁹Pu in aqueous samples at concentrations as low as 10^–10M. This nuclear counting technique utilizes the uranium L X-rays, which follow the alpha-decay of plutonium. Because L X-rays are specific for the element and not for the individual isotope, the isotopic composition of the plutonium sample must be known. The counting efficiency in the 11–23 keV range is determined from a plutonium standard, and the concentration of the sample is then calculated from the L X-ray count and the isotopic composition. The total L X-ray count is corrected for possible contributions from other radionuclides present as impurities by measuring the low-energy gamma-spectrum for each contaminant to establish specific photon/X-ray ratios. The ratios are important when²⁴¹Pu and²⁴²Pu are measured, because the respective decay chain members produce non-U L X-rays. This new method can replace the use of labor-intensive radiochemical separation techniques and elaborate activation methods for analysis of²³⁹Pu in aqueous samples. It is also applicable for assaying plutonium in liquid wastes that pose possible hazards to the environment.     

Actinides in the near release from the Chernobyl NPP accident

Actinide elements concentrations in the products of near release from CNPP accident were estimated. The data on uranium,²³⁷Np,²⁴¹Am and plutonium and curium isotopes content in fuel particles are given. Sums of -emitting radionuclides and plutonium isotopes in reactor graphite particles and of uranium,²⁴²Cm,^239+240Pu isotopes in the soil and aerosol samples were also determined. By 1989 soil and dust contamination in near release of the accident is due to long-lived -emitting plutonium isotopes.     

Application of isotope-dilution laser ablation ICP–MS for direct determination of Pu concentrations in soils at pg g<Superscript>−1</Superscript> levels

The methods available for determination of environmental contamination by plutonium at ultra-trace levels require labor-consuming sample preparation including matrix removal and plutonium extraction in both nuclear spectroscopy and mass spectrometry. In this work, laser-ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) was applied for direct analysis of Pu in soil and sediment samples. Application of a LINA-Spark-Atomizer system (a modified laser ablation system providing high ablation rates) coupled with a sector-field ICP–MS resulted in detection limits as low as 3×10^–13 g g^–1 for Pu isotopes in soil samples containing uranium at a concentration of a few g g^–1. The isotope dilution (ID) technique was used for quantification, which compensated for matrix effects in LA–ICP–MS. Interferences by UH⁺ and PbO₂⁺ ions and by the peak tail of ²³⁸U⁺ ions were reduced or separated by use of dry plasma conditions and a mass resolution of 4000, respectively. No other effects affecting measurement accuracy, except sample inhomogeneity, were revealed. Comparison of results obtained for three contaminated soil samples by use of -spectrometry, ICP–MS with sample decomposition, and LA–ICP–IDMS showed, in general, satisfactory agreement of the different methods. The specific activity of ^239+240Pu (9.8±3.0 mBq g^–1) calculated from LA–ICP–IDMS analysis of SRM NIST 4357 coincided well with the certified value of 10.4±0.2 mBq g^–1. However, the precision of LA–ICP–MS for determination of plutonium in inhomogeneous samples, i.e. if "hot" particles are present, is limited. As far as we are aware this paper reports the lowest detection limits and element concentrations yet measured in direct LA–ICP–MS analysis of environmental samples.Sergei F. Boulyga is on leave from The Radiation Physics and Chemistry Problems Institute, 220109 Sosny, Minsk, Belarus.